CN114605630A - Rapid synthesis method of thermoplastic polycaprolactone - Google Patents
Rapid synthesis method of thermoplastic polycaprolactone Download PDFInfo
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 34
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 34
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 22
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 22
- 238000001308 synthesis method Methods 0.000 title claims abstract description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000000977 initiatory effect Effects 0.000 claims abstract description 21
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 17
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- -1 alcohol compound Chemical class 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 17
- 230000035484 reaction time Effects 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- CMOXTMGJZNCXEI-UHFFFAOYSA-N 1-phenyl-2-pyridin-2-ylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=N1 CMOXTMGJZNCXEI-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
- C08G69/20—Anionic polymerisation characterised by the catalysts used
Abstract
The invention discloses a rapid synthesis method of thermoplastic polycaprolactone, which comprises the steps of carrying out ring-opening polymerization reaction on an epsilon-caprolactone monomer in a catalytic initiation system containing organic metal alcohol compounds to obtain thermoplastic polycaprolactone with high molecular weight and narrow distribution; the method adopts organic stannous alcohol compounds as a catalytic initiation system, and has the advantages of high catalytic activity, mild catalytic reaction conditions, short reaction time, high caprolactone conversion rate, less catalyst dosage, low cost and contribution to large-scale use.
Description
Technical Field
The invention relates to a method for synthesizing polycaprolactone, in particular to a method for quickly synthesizing thermoplastic polycaprolactone with narrow distribution, high molecular weight and low residue, belonging to the technical field of polycaprolactone resin synthesis.
Background
The thermoplastic polycaprolactone has the advantages of good biodegradability, biocompatibility, shape memory property and the like, and can be used as a medical orthopedic splint, a medical positioning film, an absorbable surgical suture, a medical bone nail, an in-vivo implanted stent and the like.
At present, caprolactone ring-opening polymerization catalysts reported in domestic and foreign documents mainly comprise titanium, aluminum and rare earth metal compound systems, active hydrogen, enzyme catalysis systems and the like, but the following defects exist in the prior reports: the catalytic activity is low, the required catalytic amount is large, and the obtained polycaprolactone has low molecular weight, wide distribution and deep color. ② the catalyst is expensive (such as rare earth metal catalyst). And the required polymerization reaction time is long. And fourthly, the reaction conditions are harsh and are mostly carried out in a vacuum drying oven. Usually adopting solution polymerization process, the steps are complicated, and the solvent needs to be recovered again.
Chinese patent (application No. CN201610186268.8) discloses a metal complex for efficient controllable ring opening of epsilon-caprolactone, in particular to thiourea metal salt, the obtained polycaprolactone has the highest molecular weight of 62800, and is suitable for bulk polymerization and melt polymerization processes of the epsilon-caprolactone, and also suitable for slow controllable polymerization in solution, but the cost of raw materials for synthesizing the thiourea metal salt is high.
Chinese patent (application No. CN201810980422.8) discloses synthesis of a beta-pyridine enamine bidentate aluminum complex and catalysis of ring-opening polymerization of epsilon-caprolactone. 2- (2-pyridyl) -acetophenone and aromatic amine containing different substituent groups are subjected to condensation reaction to obtain a ligand containing two nitrogen atoms, and the ligand is coordinated with alkyl aluminum to synthesize the beta-pyridine enamine bidentate aluminum metal complex. The catalyst can be used for catalyzing ring-opening polymerization reaction of epsilon-caprolactone, the polymerization reaction temperature is 70-80 ℃, the reaction time is 20-240 min, and the highest molecular weight is 35757. The method has more working procedures and lower molecular weight of the product.
Chinese patent (application No. CN200910165299.5) discloses a method for synthesizing polycaprolactone, which is completed by one-step reaction, namely end alkynyl linear or fan-shaped structure polycaprolactone is prepared by initiating the ring-opening polymerization of caprolactone body by 1 generation-3 generation alkynyl poly (amide-amine). The polymerization temperature is 130 ℃, the reaction time is 24 hours, and the highest yield of polycaprolactone is 92.2%. The method requires a longer reaction time and has a lower yield.
Mary F.Mahon et al (Inorganic Chemistry 2006,45(5): 2282-The diffraction research is characterized, the electronic effect and the space effect of the ligand are researched, the novel compound aryloxy titanium is used for ring-opening polymerization of epsilon-caprolactone to obtain polycaprolactone, the highest yield is 79 percent at room temperature, the molecular weight distribution is narrow (1.13-1.27), and the highest number average molecular weight M isnIs 4600. The polycaprolactone obtained by the method has low molecular weight and low yield.
Disclosure of Invention
Aiming at the defects of the ring-opening polymerization of polycaprolactone in the prior art, the invention aims to provide a method for quickly synthesizing thermoplastic polycaprolactone, which has the following characteristics: firstly, the used composite catalytic initiation system is safe and efficient, high in catalytic activity, low in dosage and low in cost; the reaction time for preparing the thermoplastic polycaprolactone by the ring-opening polymerization of the epsilon-caprolactone is short; thirdly, the reaction condition is mild, and bulk polymerization is realized; fourthly, the obtained thermoplastic polycaprolactone has high molecular weight and narrow distribution. High caprolactone conversion rate.
In order to realize the technical purpose, the invention provides a rapid synthesis method of thermoplastic polycaprolactone, which comprises the steps of carrying out ring-opening polymerization reaction on an epsilon-caprolactone monomer in a catalytic initiation system containing organic metal alcohol compounds to obtain the thermoplastic polycaprolactone;
the organic metal alcohol compound has a structure shown in a formula 1 and/or a formula 2:
HO-R1-O-M-O-R1-OH
formula 1
Wherein, the first and the second end of the pipe are connected with each other,
m is Sn;
R1is C2～C20An alkyl chain of (a);
R2is C1～C15An alkyl chain of (2).
The method is characterized in that a special organic metal alcohol compound catalytic initiation system is adopted, the catalytic initiation system has particularly high catalytic initiation activity for ring-opening polymerization of epsilon-caprolactone, the dosage of a catalyst is reduced, the catalytic reaction time is shortened, the monomer conversion rate of the epsilon-caprolactone is improved, meanwhile, the molecular weight of polycaprolactone can be improved, the molecular weight distribution is narrow, and the method has obvious technical advantages compared with the existing catalytic initiation system.
As a preferred embodiment, R1Is C2～C10A linear alkyl chain of (C)3～C10A branched alkyl chain; straight chain alkyl chains such as:
etc.; branched alkyl chains such as:
and so on.
As a preferred embodiment, R2Is C1～C10Of a linear alkyl chain or C3～C10A branched alkyl chain; straight alkyl chains such as methyl, ethyl, propyl, octyl, and the like; branched alkyl chains, e.g.
And so on.
As a more preferable scheme, the organic metal alcohol compound is a stannol compound a and/or a stannol compound b, wherein the structure of the stannol compound a is shown as formula 3, and the structure of the stannol compound b is shown as formula 4;
as a preferred embodiment, the weight of the catalytic initiation system comprising the organometallic alcohol compound is 1 to 2% of the weight of the epsilon-caprolactone monomer. The weight of the catalytic initiation system containing the organic metal alcohol compound is more preferably 1.3-1.7 per thousand of the weight of the epsilon-caprolactone monomer.
As a preferred embodiment, the conditions of the ring-opening polymerization are: under the protection of nitrogen, the temperature is 130-180 ℃, and the time is 20-150 minutes. The conditions of the ring-opening polymerization reaction are further preferably: the temperature is 150-170 ℃, and the time is 30-120 minutes.
The organic metal alcohol compound is obtained by reacting a diol compound with an organic acid stannous salt. The organic metal alcohol compounds with the structures shown in the formula 1 and/or the formula 2 can be formed by utilizing the chemical reaction between the diol compound and the stannous salt of the organic acid, and both the organic metal alcohol compounds are high-activity catalytic initiators for the ring-opening polymerization of epsilon-caprolactone monomers. Particularly, the reaction product obtained by the reaction can be directly used for catalyzing the ring-opening polymerization of the epsilon-caprolactone monomer without special purification and separation. The mass ratio of the diol compound to the stannous organic acid salt is 2: 1-1: 2, preferably 8: 5-1: 1. In the preferable ratio range, the sufficient reaction between the diol compound and the stannous salt of organic acid is facilitated to increase the production ratio of the metal alcohol compound of organic acid. The specific reaction conditions are as follows: the temperature is 110-120 ℃, and the time is 80-120 minutes.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
according to the technical scheme, a special catalytic initiation system is adopted, the method is safe and efficient, the reaction speed is high, the caprolactone conversion rate is high, the time can be shortened to be below 120 minutes under the condition of 150-170 ℃, the high molecular weight thermoplastic polycaprolactone can be quickly synthesized, the weight average molecular weight exceeds 100000, the molecular weight distribution index can be as low as 1.29, and the melting point is 55-62 ℃. Compared with other methods for producing polycaprolactone, the catalytic initiation system adopted by the technical scheme of the invention has the advantages of high activity, small using amount, high reaction speed, short reaction time, low cost and the like.
The technical scheme of the invention can adopt a bulk polymerization method, the production process is simple, the product chromaticity is good, and the molecular weight of the product thermoplastic polycaprolactone is high.
Drawings
FIG. 1 is a NMR spectrum of mixture A prepared in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the thermoplastic polycaprolactone prepared in examples 2-6.
FIG. 3 is a GPC chart of the thermoplastic polycaprolactone prepared in example 5.
Detailed Description
The present invention will be described in detail with reference to examples. The embodiment is implemented on the premise of the technical scheme of the invention, and gives a detailed implementation mode and a specific operation process.
Example 1
Weighing 4.81g of 2-methyl-1, 3-propylene glycol, 14.23g of stannous octoate, adding magnetons, weighed 2-methyl-1, 3-propylene glycol and stannous octoate into a 100ml three-mouth flask, installing a thermometer, firstly blowing by using nitrogen, quickly covering a rubber plug, starting the magnetons for stirring (150r/min), after the system is sealed, heating a heating jacket, controlling the temperature of liquid in the three-mouth flask to be 110-120 ℃, reacting for 100 minutes, stopping heating, installing a condensing tube, connecting a vacuum pump, starting the vacuum pump, keeping the vacuum degree at 0.085MPa, vacuumizing for 20 minutes, discharging to obtain a mixture containing a tin alcohol compound a, a tin alcohol compound b, residual stannous octoate and 2-methyl-1, 3-propylene glycol, referred to as a mixture A for short, used without purification.
Example 2
200g of epsilon-caprolactone is weighed and poured into a three-neck flask. Weighing 0.32g (monomer and weight ratio thereof is 1.60 per thousand) of a mixture A (catalytic initiation system) containing a tin alcohol compound a, a tin alcohol compound b, stannous octoate and 2-methyl-1, 3-propylene glycol, adding the mixture A into a three-mouth flask, installing a thermometer, a condenser pipe, a metal stirring rod and the like, introducing nitrogen, opening a condensed water inlet and a condensed water outlet, starting a stirring device, heating a heating jacket after the system is sealed, controlling the liquid temperature in the three-mouth flask to be 150-170 ℃, reacting for 30 minutes, discharging, wherein the product is pure white in color, the molecular weight and the molecular weight distribution index of the product are measured by a GPC gel chromatograph, the weight average molecular weight of the obtained product is 105179, the molecular weight distribution index is 1.29, the conversion rate of caprolactone is 88.89%, and the nuclear magnetic resonance hydrogen spectrum of the product is shown in figure 2.
Example 3
200g of epsilon-caprolactone is weighed and poured into a three-neck flask. Weighing 0.32g (monomer and mass ratio thereof is 1.60 per thousand) of a mixture A (catalytic initiation system) containing a tin alcohol compound a, a tin alcohol compound b, stannous octoate and 2-methyl-1, 3-propylene glycol, adding the mixture A into a three-mouth flask, installing a thermometer, a condenser pipe, a metal stirring rod and the like, introducing nitrogen, opening a condensed water inlet and a condensed water outlet, starting a stirring device, heating a heating jacket after the system is sealed, controlling the liquid temperature in the three-mouth flask to be 150-170 ℃, reacting for 60 minutes, discharging, wherein the product is pure white in color, the molecular weight and the molecular weight distribution index of the product are measured by a GPC gel chromatograph, the weight average molecular weight of the obtained product is 120632, the molecular weight distribution index is 1.42, the conversion rate of caprolactone is 98.35%, and the nuclear magnetic resonance hydrogen spectrum of the product is shown in figure 2.
Example 4
200g of epsilon-caprolactone is weighed and poured into a three-neck flask. Weighing 0.32g (monomer and 1.60 per mill of mass ratio thereof) of a mixture A (catalytic initiation system) containing a tin alcohol compound a, a tin alcohol compound b, stannous octoate and 2-methyl-1, 3-propylene glycol, adding the mixture A into a three-mouth flask, installing a thermometer, a condenser pipe, a metal stirring rod and the like, introducing nitrogen, opening a condensed water inlet and outlet, starting a stirring device, after the system is determined to be sealed, heating a heating jacket, controlling the liquid temperature in the three-mouth flask to be 150-170 ℃, reacting for 90 minutes, discharging, wherein the product is pure white, the molecular weight and molecular weight distribution index of the product are measured by a GPC (gel permeation chromatography) gel chromatograph, the weight average molecular weight of the obtained product is 124529, the molecular weight distribution index is 1.39, the caprolactone conversion rate is 98.61%, and the nuclear magnetic resonance hydrogen spectrum of the product is shown in an attached figure 2.
Example 5
200g of epsilon-caprolactone is weighed and poured into a three-neck flask. Weighing 0.32g (monomer and 1.60 per thousand of the mass ratio) of a mixture A (catalytic initiation system) containing a tin alcohol compound a, a tin alcohol compound b, stannous octoate and 2-methyl-1, 3-propylene glycol, adding the mixture A into a three-mouth flask, installing a thermometer, a condenser pipe, a metal stirring rod and the like, introducing nitrogen, opening a condensed water inlet and a condensed water outlet, starting a stirring device, heating a heating jacket after the system is sealed, controlling the temperature of liquid in the three-mouth flask to be 150-170 ℃, reacting for 120 minutes, discharging, wherein the product is pure white, the molecular weight and the molecular weight distribution index of the product are measured by a GPC gel chromatograph, the weight average molecular weight of the obtained product is 133070, the molecular weight distribution index is 1.30, the GPC spectrogram is shown in figure 3, the caprolactone is 99.16%, and the nuclear magnetic resonance hydrogen spectrum of the product is shown in figure 2.
Example 6
200g of epsilon-caprolactone is weighed and poured into a three-neck flask. 0.32g (monomer and mass ratio thereof is 1.60 per thousand) of a mixture A (catalytic initiation system) containing a tin alcohol compound a, a tin alcohol compound b, stannous octoate and 2-methyl-1, 3-propylene glycol is weighed and added into a three-mouth flask, installing a thermometer, a condenser pipe, a metal stirring rod and the like, introducing nitrogen, opening a condensed water inlet and a condensed water outlet, starting a stirring device, determining that the system is sealed, heating the heating jacket, controlling the temperature of liquid in the three-neck flask to be 150-170 ℃, reacting for 120 minutes, vacuumizing, keeping the vacuum degree at 0.085MPa, discharging after vacuumizing for 15 minutes, wherein the product is pure white, the molecular weight and the molecular weight distribution index of the product are measured by a GPC (gel permeation chromatography) gel chromatograph, the weight average molecular weight of the obtained product is 129248, the molecular weight distribution index is 1.33, the conversion rate of caprolactone is 99.14%, and the nuclear magnetic resonance hydrogen spectrum of the product is shown in figure 2.
The invention is subsidized by the scientific and technological innovation plan of Hunan province, and the project number is as follows: 2021RC 3138; the invention is subsidized by the limited company of the China petrochemical industry group.
Claims (7)
1. A rapid synthesis method of thermoplastic polycaprolactone is characterized in that: the epsilon-caprolactone monomer is subjected to ring-opening polymerization reaction in a catalytic initiation system containing organic metal alcohol compounds to obtain the epsilon-caprolactone monomer;
the organic metal alcohol compound has a structure shown in a formula 1 and/or a formula 2:
HO-R1-O-M-O-R1-OH
formula 1
Wherein the content of the first and second substances,
m is Sn;
R1is C2～C20A hydrocarbon chain of (a);
R2is C1～C15A hydrocarbon chain of (2).
2. The method for rapidly synthesizing the thermoplastic polycaprolactone according to claim 1, characterized in that:
R1is C2～C10Of a linear alkyl chain or C3～C10A branched alkyl chain;
R2is C1～C10Of a linear alkyl chain or C3～C10A branched alkyl chain.
3. The method for rapidly synthesizing the thermoplastic polycaprolactone according to claim 2, characterized in that:
the organic metal alcohol compound has a structure shown in a formula 3 and/or a formula 4:
4. the method for rapidly synthesizing the thermoplastic polycaprolactone according to any one of claims 1-3, characterized in that: the weight of the catalytic initiation system containing the organic metal alcohol compound is 1-2 per mill of the weight of the epsilon-caprolactone monomer.
5. The method for rapidly synthesizing the thermoplastic polycaprolactone according to claim 4, characterized in that: the weight of the catalytic initiation system containing the organic metal alcohol compound is 1.3-1.7 per mill of the weight of the epsilon-caprolactone monomer.
6. The method for rapidly synthesizing the thermoplastic polycaprolactone according to any one of claims 1-3, characterized in that: the conditions of the ring-opening polymerization reaction are as follows: under the protection of nitrogen, the temperature is 130-180 ℃, and the time is 20-150 minutes.
7. The method for rapidly synthesizing the thermoplastic polycaprolactone according to claim 6, characterized in that: the conditions of the ring-opening polymerization reaction are as follows: the temperature is 150-170 ℃ and the time is 30-120 minutes.
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